KR20140116100A - Non-precious metal-based hydrosilylation catalysts - Google Patents

Abstract

The present invention relates to the use of manganese, iron, cobalt or nickel complexes comprising a tri-coordinated pyridine diimine ligand as the hydrosilylation catalyst, and these complexes not only efficiently promote the hydrosilylation reaction, Lt; RTI ID = 0.0 > and / or < / RTI > catalyst systems.

Description

NON-PRECIOUS METAL-BASED HYDROSILYLATION CATALYSTS < RTI ID = 0.0 >

The present invention relates generally to the use of transition metal-containing compounds, and more particularly to the use of manganese, iron, and zirconium containing a tridentate pyridine diimine ligand as a seletive hydrosilylation catalyst, Cobalt, or nickel complexes.

The hydrosilylation chemistry typically involves the reaction between a silylhydride and an unsaturated organic group may be used in commercial silicon-based products such as silicone surfactants, silicone fluids and silanes, as well as sealants, adhesives, ≪ / RTI > is the basis of synthetic routes to produce a number of additional cure products, such as < RTI ID = 0.0 > To date, hydrosilylation reactions have typically been promoted with noble metal catalysts such as platinum or rhodium metal complexes.

Various noble metal complex catalysts are known in the art. For example, U.S. Patent No. 3,775,452 discloses platinum complexes containing an unsaturated siloxane as a ligand. This type of catalyst is known as a Karstedt's catalyst. Other representative platinum-based hydrosilylation catalysts disclosed in the literature include the Ashby's catalyst described in U.S. Patent No. 3,159,601, Lamoreaux's catalyst described in U.S. Patent No. 3,220,972, There is a Speier's catalyst described in Speier, et al., J. Am. Chem. Soc, 1957, 79, 974.

Recently, it has been found that new low-cost, non-noble metal-based complexes containing a three-coordinate coordinating nitrogen ligand selectively catalyze the hydrosilylation reaction, as disclosed in U.S. Patent Application Publication No. 2011/0009573 and No. 2011 / 0009565. Both of which are incorporated herein by reference in their entirety. In addition to low cost and selectivity, these catalysts have the advantage that hydrosilylation can only catalyze hydrosilylation at room temperature while noble metal catalysts typically operate at elevated temperatures.

Five-coordinate Fe (II) complexes containing a pyridinediamine (PDI) ligand having an isopropyl substituent at the ortho position of an aniline ring were synthesized using PhSiH ₃ (1-hexene) with primary and secondary silanes such as Ph ₂ SiH ₂ (Bart, et al, J. Am. Chem. Soc, 2004, 126, 13794) (Archer , et al., Organometallics, 2006, 25, 4269). However, these catalysts were found to be effective only for the primary and secondary phenyl-substituted silanes described above, and not for alkoxy substituted silanes such as (EtO) ₃ SiH.

In one embodiment, the invention relates to a process for hydrosilylation of a composition comprising silyl hydride and at least one unsaturated group-containing compound.

The method comprises the steps of (i) contacting the composition with a complex of formula (I) in the presence or absence of a solvent to cause the silyl hydride to react with the at least one unsaturated group-containing compound, Producing a hydrosilylation product; And (ii) optionally opιcally removing the complex from the hydrosilylation product.

(식 I)

(Formula I)

here:

G is Mn, Fe, Ni, or Co;

x is O or 1;

Each R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ And R _9` are independently H, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group;

Each R ₃ is independently H, C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, or an inert functional group, wherein R ₁ to R ₉ other than hydrogen optionally contain at least one heteroatom;

Each R ₁₀ is C ₁ -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl or substituted aryl group, optionally containing at least one heteroatom;

Any _two of which are optionally adjacent to each other of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may be substituted or unsubstituted, saturated or unsaturated To form a ring which is a cyclic structure.

The silyl hydride is _{^{R 3 a (R 4 0)}} b SiH ( formula _Ⅱ), Q _u T _v T _p ^H D _w D ^H _x M ^H _y M _z (formula _{Ⅲ), R 3 Si (CH} 2) f (SiR ₂ O) _e SiR ₂ H (Formula XX), (RO) ₃ Si (CH ₂ ) _f (SiR ₂ O) _e SiR ₂ H (Formula XXI), and combinations thereof;

Wherein Q is Si0 _4/2, T is a R'Si0 _3/2 and, T ^H is HSi0 _3/2, and, D is R _'2 Si0 _2/2, and, D is ^H R'HSi0 _2/2, M is ^H H _g R _{'3 -,} and _g Si0 _1/2, M is R' ₃ Si0 _1/2 a.

Each R ³ , R ⁴ and R 'is independently C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl, or substituted aryl wherein R ³ , R ⁴ And R 'optionally comprise at least one heteroatom;

a and b are integers of from 0 to 3, with the proviso that a + b = 3; f has a value of 1 to 8, e has a value of 1 to 11, each g has a value of 1 to 3, p is 0 to 20, u is 0 to 20, v is 0 to 20 X is 0 to 1000, y is 0 to 20, and z is 0 to 20 with the proviso that p + x + y is 1 to 3000, and all the elements of the silylhydride are It is assumed that the valence satisfies.

The at least one unsaturated group-containing compound is selected from the group consisting of alkene, C2-C18 olefins, cycloalkenes, unsaturated cycloalkanes, unsaturated cycloalkenes, unsaturated cycloalkyl epoxides, unsaturated alkyl epoxides, end unsaturated amines, unsaturated aromatic hydrocarbons, Selected from the group consisting of allyl polyether, unsaturated aryl ethers, vinyl-functionalized silanes, vinyl-functionalized silicones, terminally unsaturated acrylates or methyl acrylates, terminally unsaturated polyurethane polymers, and combinations thereof.

However, when the complex of formula (I) is iron, bis (dinitrogen) [N, N '- [(2,6-pyridinediyl 虜 N) diethylidine] bis [2,6- Benzeneamine-kappa]] -, (SP-5-13) -coordinate compound and the silylhydride is triethylsilane, the at least one unsaturated group-containing compound is an alkyl capped allyl polyether or styrene; And the complex of formula (I) is selected from the group consisting of iron, bis (dinitrogen) [N, N '- [(2,6-pyridinediyl 虜 N) diethylidine] bis [2,6- Amine-kappa]] -, (SP-5-13) -coordinate compound, and if the silylhydride is methylbis (trimethylsilyloxy) silane, the at least one unsaturated group-containing compound is an alkyl capped allyl polyether Can not be.

In the present invention, iron, bis (dinitrogen) [N, N '- [(2,6-pyridinediyl 虜 N) diethylidine] bis [2,6- ] -, (SP-5-13) - The coordination compound is represented by ( ^iPr PDI) Fe (N ₂ ) ₂ . Its structure is presented in the introductory part of the examples below.

In another aspect, the present invention relates to a hydrosilylation process for a composition comprising a silylhydride and at least one unsaturated group-containing compound using a complex of formula (XIX) as catalyst.

The complexes of formula (XIX) are as follows:

(식 XIX)

(Formula XIX)

here,

G is Mn, Fe, Ni, or Co;

x is O or 1;

Each R & _{lt ; 1 & gt;} R _2, R ₄ , R 5, R ₆ , R ₇ , R ₈ and R ₉ are independently H, C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl, substituted aryl, or an inert functional group;

Each R < ₁₅ > is aryl or substituted aryl;

R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₅ other than hydrogen optionally contain at least one heteroatom;

Each R ₁₀ is C ₁ -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl or substituted aryl group, wherein R ₁₀ optionally contains at least one heteroatom;

Any _two of the adjacent ones of R ₁ , R ₂ , R ₁₅ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may optionally be substituted or unsubstituted, To form a ring of a cyclic structure.

With respect to the hydrosilylation method of using the complex of the formula (XIX) as the catalyst, a suitable silyl hydride (R ⁴ 0) ₃ SiH and (wherein XXⅡ), wherein each R ⁴ is independently a C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, and R < ⁴ > optionally includes at least one heteroatom. Advantageously, said at least one unsaturated group-containing compound is selected from the group consisting of terminal unsaturated amines, unsaturated aromatic hydrocarbons, unsaturated cycloalkanes, and combinations thereof.

In another aspect, the invention is directed to a method for selectively producing a mono-hydrosilylation product from a composition comprising a silylhydride and a polyunsaturated compound. Said method comprising contacting said composition with a complex of formula (I) or formula (XIX) as defined above to react said silylhydride with said polyunsaturated compound, wherein the hydrosilylation occurs selectively at one of said unsaturated groups To yield a mono-hydrosilylation product. In connection with this method, the polyunsaturated compound is represented by formula (VII) or formula (VIII)

E ¹ [(CH ₂ ) _β CR ¹ = CH ₂ ] _α (Formula VII)

R ² _? E ² [(CH ₂ ) _? CR ¹ = CH ₂ ] _? (Formula VIII)

Wherein E ¹ is a divalent or polyvalent aliphatic or aromatic cyclic hydrocarbon group containing from 3 to 25 carbon atoms or a divalent or polyvalent aliphatic or aromatic heterocyclic group containing from 3 to 25 carbon atoms Wherein the heteroatom is selected from the group consisting of oxygen, nitrogen, silicon and sulfur;

E ² is a divalent or polyvalent cyclic silicon group containing 3 to 8 silicon atoms and 3 to 8 oxygen atoms;

Each R ¹ and R ² is independently hydrogen or a hydrocarbon group containing from 1 to 8 carbon atoms;

Each?,? And? Are independently integers, wherein? Is 2 to 6; beta is 0 to 6; y is from 0 to 4;

Advantageously, with respect to the selective mono-hydrosilylation process described above, the molar ratio of Si-H functional groups in the silylhydride to the alkenyl functionality in the unsaturated compound is from about 0.5 / alpha to about 1.1 / alpha / RTI >

These and other aspects will become apparent from the following detailed description of the invention.

The complexes according to formulas (I) and (XIX) are effective in promoting hydrosilylation of sterically hindered silanes such as alkoxy-substituted silanes such as (EtO) ₃ SiH and methylbis (trimethylsilyloxy) silane. In addition, the complexes have unexpected improvements in the selectivity of the mono-hydrosilylation of polyunsaturated substrates such as trivinylcyclohexane over both the platinum-based catalyst and FePDI complexes described in U.S. Patent Application Publication No. 2011/0009573 .

The complexes of formulas (I) and (XIX) are described above. With respect to these equations, G may be Mn, Fe, Ni, or Co. Preferably, G is iron or cobalt. More preferably, G is Fe (II).

The term "alkyl" as used herein includes linear, branched and cyclic alkyl groups. Certain non-limiting alkyls include, but are not limited to, methyl, ethyl, propyl, and isobutyl. Unless otherwise indicated, alkyl groups suitable for the present invention are C1-C18 alkyl, specifically C1-C10 alkyl, more particularly C1-C6 alkyl.

"Substituted alkyl" as used herein refers to an alkyl group containing one or more substituents, wherein the substituent is a substituent that is inert under the conditions of the process of the invention under which the compound containing the substituent is subjected. In addition, the substituent does not substantially interfere with the hydrosilylation process described in the present invention. Unless otherwise stated, such substituents suitable for the present invention are C1-C18 substituted alkyl, specifically C1-C10 substituted alkyl, more particularly C1-C6 substituted alkyl. In one embodiment, the substituent is an inert functional group as defined herein.

As used herein, the term "aryl" means a non-limiting group of any aromatic hydrocarbon from which one hydrogen atom has been removed. Aryl may have one or more aromatic rings, which may be linked by a single bond or by another group. Specific non-limiting examples of aryl include, but are not limited to, tolyl, xylyl, phenyl, and naphthyl.

The term "substituted aryl" as used herein refers to an aromatic group containing one or more substituents, wherein the substituent is a substituent that is inert under the conditions of the process of the invention under which the compound containing the substituent is subjected. In addition, the substituent does not substantially interfere with the hydrosilylation process described in the present invention. As with aryl, substituted aryl may have at least one aromatic ring, which may be linked by a single bond or another group, but with the substituted aryl a heteroaromatic ring, the free valencies in the substituted aryl group may be replaced by hetero (E. G., Nitrogen) of the aromatic ring. Unless otherwise indicated, the substituents of the substituted aryl group include from 0 to about 30 carbon atoms, specifically from 0 to 20 carbon atoms, and more specifically from 0 to 10 carbon atoms. In one embodiment, the substituent is an inert functional group as defined herein.

The term "unsaturated" means one or more double or triple bonds. Advantageously, it refers to a carbon-carbon double or triple bond.

As used herein, the term "inert functional group" is a group other than alkyl, substituted alkyl, aryl or substituted aryl, which is inert under the conditions of the process of the invention under which the compound containing this group is subjected. In addition, the inert functional groups do not substantially interfere with the hydrosilylation process described in the present invention. Examples of inert functional groups include ethers such as halo (fluoro, chloro, bromo, and iodo), -OR ³⁰ , where R ³⁰ is hydrocarbyl or substituted hydrocarbyl. Advantageously, the inert functional group is a halo group.

The term "heteroatom" means any of the 13-17 group elements excluding carbon, such as oxygen, nitrogen, silicon, sulfur, phosphorus, fluorine, chlorine, bromine, and iodine.

의 페닐이다: In some embodiments, the complexes according to the present invention are those of formulas (I) and (XIX) having the following substituents: (1) R ₁ is isopropyl, t-butyl, cyclohexyl, or cyclopentyl; And / or (2) R ₁ and R ₂ are both isopropyl, t-butyl, cyclohexyl or cyclopentyl; And / or (3) R ₃ is methyl in relation to formula (I) and phenyl in relation to formula (XIX); And / or (4) R ₄ R ₉ is hydrogen; And / or (5) R < ₁₀ > is C1-C10 alkyl or

Lt; / RTI >

Various methods can be used to prepare the complexes of formulas (I) and (XIX). One method involves reacting the metal-PDI dihalide complex with sodium in the presence of mercury and nitrogen. The metal-PDI dihalide complex can be prepared by reacting a PDI ligand with a metal halide (e.g., FeBr ₂ ). Typically, the PDI ligand is produced through the condensation reaction of an appropriate amine or aniline with 2,6-diacetylpyridine and its derivatives. If desired, the PDI ligand may be further modified by known aromatic displacement chemistry. Representative methods for preparing complexes of formulas (I) and (XIX) can be found in Bart, et al., J. Am. Chem. Soc, 2004, 126, 13794, The entire contents of which are incorporated herein by reference.

The metal complexes of formulas (I) and (XIX) are useful for promoting industrially practiced hydrosilylation reactions, and in particular for the preparation of (1) silicone hydride fluids and vinyl end- Bridging; And (2) hydrosilylation of allylamine and tertiary silane for use as adhesion promoters and coupling agents.

When used as a catalyst for the hydrosilylation reaction, the complexes of the above formulas (I) and (XIX) are unsupported or can be supported by, for example, silica, alumina, MgCl ₂ Or zirconia, or to a polymer or prepolymer such as, for example, polyethylene, polypropylene, polystyrene, or poly (aminostyrene).

In some embodiments, it is preferred for the purposes of attaching the complexes of formulas (I) and (XIX) to the support that at least one of R ₇ , R ₈ and R ₉ of said metal complexes having structural formula (I) One having a functional group that is covalently bonded to the carrier effectively. Representative, but non-limiting, examples of the functional groups is SH, COOH, NH ₂ Or an OH group.

In certain embodiments, the silica-supported complexes of the present invention can be prepared by methods known in the art, for example, in the literature "Macromol. Chem. Phys., 2001, 202, No. 5, 645" and "Journal of Chromatography A, 1025, 2003, And can be produced by Ring-Opening Metathesis Polymerization (ROMP) technique described above. The foregoing description of the above documents is incorporated herein by reference in its entirety.

In some embodiments, the complex of formula (I) or (XIX) is prepared by reacting Si-Cl (XIX) in the presence of a base as illustrated in Kim, et al., Journal of Organometallic Chemistry 673, 2003, Can be immobilized on the surface of the dendrimer by reaction of the coupled dendrimers with the functionalized complexes of the formulas (I) and (XIX).

The hydrosilylation reaction according to the invention may optionally be carried out in the presence of a solvent. Suitable, but non-limiting, examples of solvents include non-polar, aliphatic and aromatic hydrocarbon solvents. Once the hydrosilylation reaction is complete, the metal complex may be removed from the reaction product by self-separation, filtration and / or extraction, if desired.

The temperature of the hydrosilylation reaction may be about -50 ° C to about 120 ° C, specifically 0 ° C to 80 ° C, more specifically 10 ° C to 60 ° C. Advantageously, the hydrosilylation reaction is carried out at room temperature (e.g., 20 ° C to 25 ° C).

When the complexes of formula (I) are used as catalysts, suitable silyl hydrides are R ³ _a (R ⁴ 0) _b SiH (formula II) _, Q _u T _v T _p ^H D _w D ^H _x M ^H _y M _z expression _{ⅲ), R 3 Si (CH} 2) f (SiR 2 0) e SiR 2 H ( formula _{XX), (RO) 3 Si} (CH 2) f (SiR 2 0) e SiR 2 H ( formula XXI), ≪ / RTI > and combinations thereof. The silyl hydride may have a linear, branched or cyclic structure, or a combination structure thereof. As used herein, each of R ³ , R ⁴ , and R 5 is independently selected from the group consisting of C 1 -C 18 alkyl, specifically C 1 -C 10 alkyl, more particularly C 1 -C 6 alkyl, C 1 -C 18 substituted alkyl, , more specifically, a C1-C6 substituted alkyl, aryl, and substituted aryl, and wherein R ^3, R ^4, and R includes at least one heteroatom in any optional. Subscripts a and b are integers from 0 to 3, provided that a + b = 3, f has a value of 1 to 8, e has a value of 1 to 11, and each of p, u, v, z has independently a value of 0 to 20, w and x are 0 to 1000, provided that p + x + y is 1 to 3000, and that all the elements of the silylhydride satisfy the valencies thereof . P, u, v, y, and z are 0 to 10, w and x are 0 to 100, wherein p + x + y is 1 Lt; / RTI > In one embodiment, a is 0 and b is 3.

A, "M" group formula R _'3 SiO _1/2, 1 indicates a functional group, "D" group is formulas R' ₂ represents a second functional group of S1O _2/2, "T" groups used herein expressions R'Si0 _{3 /} represents a 3-functional groups of _2, "Q" group is formulas S1O of the _4/2 represents the 4 functional group, "M ^H" groups are H _g R _{'3 -} represents a _{g SiO 1/2, "T} H" is HSi0 _3/2 represents a, "D ^H" group refers to a R'HSi0 _2/2. As used herein, g is an integer from 0 to 3. Each R 'is independently selected from C1-C18 alkyl, specifically C1-C10 alkyl, more particularly C1-C6 alkyl, C1-C18 substituted alkyl, specifically C1-C10 substituted alkyl, Aryl, and substituted aryl, wherein R 'optionally includes at least one heteroatom.

In some embodiments, the silylhydride has the structure of formula (IV) or formula (V): < EMI ID =

(식 IV)

(Formula IV)

(식 V)

(Formula V)

Wherein each R ⁷ , R ⁸ and R ⁹ is independently C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl, or substituted aryl, and R ⁶ is selected from the group consisting of hydrogen, C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, Or substituted aryl, w and x are independently 0 or greater than zero.

In other embodiments, a suitable silyl hydride _{(CH 3 0) 3 SiH,} (C 2 H 5 0) 3 SiH, (CH 3) 3 SiOSi (CH 3) 2 H, [(CH 3) 3 SiO] ₂ SiH (CH ₃ ), [(CH ₃ ) ₂ SiO] ₃ OSiH (CH ₃ ) and [(CH ₃ ) ₂ SiO] ₄ OSiH (CH ₃ ).

In connection with the method of using the complex of formula (I) as catalyst, said at least one unsaturated group-containing compound is selected from the group consisting of alkyne, C2-C18 olefins, cycloalkenes, unsaturated cycloalkanes, unsaturated cycloalkenes, Functionalized silanes, vinyl-functionalized silicones, terminally unsaturated acrylates or methyl acrylates, polyunsaturated polyesters, polyunsaturated polyesters, polyunsaturated polyesters, polyunsaturated polyesters, polyunsaturated polyesters, polyunsaturated polyesters, polyunsaturated polyesters, polyunsaturated polyesters, polyunsaturated polyesters, Urethane polymers, and combinations thereof.

The alkenes suitable for the hydrosilylation reaction are not particularly limited. Advantageously, suitable olefins are C2-C18 alpha olefins such as 1-octene. Representative examples of terminally unsaturated amines include allylamine and N, N-dimethylallylamine. Exemplary unsaturated cycloalkyl epoxides include vinylcyclohexyl epoxides such as limonene oxide and 4-vinyl-1-cyclohexene 1,2-epoxide. Exemplary unsaturated alkyl epoxides include, but are not limited to, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, butadiene monoxide, Hexene, and allyl glycidyl ether. An example of a representative unsaturated cycloalkane includes trivinylcyclohexane. Exemplary unsaturated aromatic compounds include styrene.

In some embodiments, the at least one unsaturated group-containing compound is selected from the group consisting of R ³ _a SiR ¹² _{4 -a} (Formula XV II), Q _u T _v T _p ^vi D _w D ^vi _x M ^vi _y M _z (Formula XVIII) and is selected from the group consisting of wherein, Q is Si0 _4/2 and, T is R'Si0 _3/2 and, T ^vi is R ¹² Si0 _3/2, and, D is R _'2 Si0 _{2 / 2,} and, D ^vi is _{^{R'R 12 Si0 2/2, M}} vi is R ¹² _g R _{'3 - g} and SiOi / _2, M is R' ₃ Si0 _1/2, and; R ¹² is vinyl; Each of R ³ and R 'are independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, wherein R ³ and R' comprises at least one heteroatom and optionally with any; a has a value of 1 to 3, each g has a value of 1 to 3, p is 0 to 20, u is 0 to 20, v is 0 to 20, w is 0 to 5000, x Is 0 to 5000, y is 0 to 20, z is 0 to 20, and v + p + w + x + y is 1 to 10,000, and all the elements in the at least one unsaturated group- It is assumed that the valence satisfies.

In other embodiments, the at least one unsaturated group-containing compound is selected from the group consisting of 1-octene, trivinylcyclohexane, styrene, alkyl capped allyl polyether, N, N-dimethylallylamine, vinyl siloxane of formula (VI) And combinations thereof.

(식 VI)

(VI)

Wherein each R ₁₁ is independently C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, vinyl, aryl, or substituted aryl, and n is 0 or greater than zero.

In some embodiments, if the silylhydride is a trialkylsilane having the formula R ₃ SiH where R is C1-C18 alkyl, specifically C1-C10 alkyl, more particularly C1-C5 alkyl, Suitable unsaturated group-containing compounds are terminally unsaturated amines such as N, N-dimethylallylamine.

When the complex of the formula (XIX) to be used as a catalyst for the hydrosilylation reaction, a suitable silyl hydride (R ⁴ 0) ₃ SiH (formula XXⅡ) (wherein each R ⁴ is independently a C1-C18 alkyl, C1- C18 substituted alkyl, aryl, or substituted aryl, and R < ⁴ > optionally includes at least one heteroatom. The at least one unsaturated group-containing compound is selected from the group consisting of allylamine, terminal unsaturated amines such as N, N-dimethylallylamine, unsaturated aromatic hydrocarbons such as styrene, unsaturated cycloalkanes such as trivinylcyclohexane, and combinations thereof It is selected from the group.

The metal complexes of formulas (I) and (XIX) are effective and selective in promoting the hydrosilylation reaction. For example, when the unsaturated group-containing compound is an end unsaturated amine, the hydrosilylation product is essentially free of internal addition products and isomerization products of the terminal unsaturated amine. As used herein, the expression "essentially free" means less than 10 wt%, preferably less than 5 wt%, based on the total weight of the hydrosilylation product. By "essentially free of internal addition products" it is meant that silicon is added to the terminal carbon of the terminal unsaturated amine.

Thus, in some embodiments, the present invention also relates to compositions prepared in the aforementioned methods. The composition comprises a compound of formula (I) or (XIX) in addition to the hydrosilylation product of the silyl hydride and at least one unsaturated group-containing compound.

In addition to promoting the hydrosilylation reaction described above, complexes of formula (I) or (XIX) are also effective for mono-hydrosilylation of polyunsaturated compounds. Thus, in one embodiment, the present invention relates to a method for selectively producing a mono-hydrosilylation product from a composition comprising a silylhydride and a polyunsaturated compound. The method comprises contacting the composition with a complex of formula (I) or (XIX), wherein the silyl hydride reacts with the polyunsaturated compound to selectively hydrosilylate at one of the unsaturated groups of the polyunsaturated compound, Lt; RTI ID = 0.0 > hydrosilylation < / RTI > product. The mono-hydrosilylation product can be removed from the reaction mixture in a subsequent step, for example, by distillation.

The polyunsaturated compound is represented by formula (VII) or formula (VIII):

E ¹ [(CH ₂ ) _β CR ¹ = CH ₂ ] _α (Formula VII)

R ² _? E ² [(CH ₂ ) _? CR ¹ = CH ₂ ] _? (Formula VIII)

With respect to Formula (VII), E ¹ is a divalent or polyvalent aliphatic or aromatic cyclic hydrocarbon group containing 3 to 25 carbon atoms, or a divalent or polyvalent group containing 3 to 25 carbon atoms Aliphatic or aromatic heterocyclic hydrocarbon. Suitable heteroatoms include, but are not limited to, oxygen, nitrogen, silicon, and sulfur. In one embodiment, E &^lt; ¹ > contains from 4 to 20 carbon atoms. In another embodiment, E &^lt; ¹ > contains from 4 to 15 carbon atoms. Representative examples of E < ¹ > include aliphatic cyclic hydrocarbons such as cyclohexyl; Aromatic cyclic hydrocarbons such as benzene rings; A heterocyclic moiety such as a cyanurate, isocyanurate, or triazine ring. Advantageously, E ¹ is a cyclohexyl or benzene ring.

With respect to formula (VIII), E ² is a divalent or polyvalent cyclic silicon group containing 3 to 8 silicon atoms and 3 to 8 oxygen atoms. Representative examples of E ² include cyclotrisiloxane rings and cyclotetrasiloxane rings.

With respect to formula (VII) and formula (VIII), each R ¹ and R ² is independently hydrogen or a hydrocarbon group containing from 1 to 8 carbon atoms. In one embodiment, R < ^{1 >} is hydrogen or a C1-C4 alkyl group. In another embodiment, R < ² > is hydrogen, a methyl or an ethyl group.

Each?,? And? Are independently integers,? Has a value of from 2 to 6, preferably from 3 to 6; beta has a value from 0 to 6, advantageously from 0 to 2; has a value of 0 to 4.

Advantageously, the polyunsaturated compound is a polyalkenyl compound. Examples of the polyalkenyl compounds include trivinylcyclohexane, trivinylbenzene, tetravinylcyclobutane, trivinyltrimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, triallyl cyanurate, and triallyl isocyanurate And trivinylcyclohexane is preferred.

Suitable as the silylhydrides used in the selective mono-hydrosilylation reaction are those mentioned above in connection with the hydrosilylation process using the complex of formula (I) as catalyst. In some embodiments, the silylhydride has one of the following structures:

R ³ _a (R ⁴ 0) _b SiH (formula II)

(식 IV)

(Formula IV)

(식 V)

(Formula V)

Wherein each R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ is independently C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl, or substituted aryl, and R ⁶ is hydrogen, C18 substituted alkyl, aryl, or substituted aryl, w and x are independently 0 or greater than 0, a and b are integers from 0 to 3, with the proviso that a + b = 3.

Representative, but non-limiting examples of silylhydrides suitable for the selective mono-hydrosilylation process of the present invention include trialkylsilanes such as (C ₂ H ₅ ) ₃ SiH, (CH ₃ O) ₃ SiH k and C tree, such as ₂ H ₅ 0) ₃ SiH _{alkoxysilane, (CH 3) 3 SiOSi (} CH 3) hydrido _{disiloxane, [(CH 3) 3 SiO} ] hydrido tree, such as the ₂ SiH (CH _3), such as 2H Siloxane, and hydridocyclosiloxanes such as [(CH ₃ ) ₂ SiO] ₃ OSiH (CH ₃ ) and [(CH ₃ ) ₂ SiO] ₄ OSiH (CH ₃ ).

In the composition to be reacted for the formation of the mono-hydrosilylation product, the molar ratio of Si-H functional groups in the silylhydride to the alkenyl functionality in the unsaturated compound is from about 0.5 / alpha to about 1.1 / alpha , Where a is an integer from 2 to 6. If the ratio is less than about 0.5 / alpha, the reaction can be terminated leaving a large amount of unreacted polyunsaturated compound. If the ratio is greater than about 1.1 / a, the reaction will produce excess bis-hydrosilylation product, which may reduce selectivity. Advantageously, the ratio is about 1 / a. The selective mono-hydrosilylation is favored by the slow addition of the silyl hydride to the reaction mixture comprising the polyunsaturated compound and the above-described non-noble metal based catalyst precursor.

The amount of the catalyst in the reaction mixture is from 1 to 10,000 ppm, specifically from 10 to 5000 ppm, more specifically from 20 to 2000 ppm, calculated on the basis of the non-noble metal catalyst precursor in the overall reaction mixture.

 The temperature of the reaction leading to the optional

The reaction temperature to induce selective mono-hydrosilylation may be from about -50 ° C to about 120 ° C, specifically from 0 ° C to 80 ° C, more specifically from 10 ° C to 60 ° C. Because the hydrosilylation is exothermic, it may be necessary to apply cooling to adjust the temperature within a narrow range depending on the specific polyunsaturated compound and the silylhydride used.

The solvent helps not only to dissolve the catalyst but also to control the reaction rate. Hydrocarbon solvents such as toluene and pentane are suitable. Selective mono-hydrosilylation is favored by dissolving the silylhydride in a solvent and slowly adding the resulting solution to the reaction mixture comprising the polyunsaturated compound and the catalyst of the present invention. An effective addition rate is a rate that minimizes both the degree of reaction exotherm and the degree of bis-hydrosilylation.

In another embodiment, the present invention relates to a composition prepared in the above-described selective mono-hydrosilylation process. In this composition, the ratio of the mono-hydrosilylation product to the bis-hydrosilylation product is greater than about 1.8, specifically greater than about 3, and more specifically greater than about 4. The composition may contain a complex of formula (I) or (XIX).

Another preferred embodiment is a composition prepared by hydrosilylation of trivinylcyclohexane. The composition comprises a monosilylated divinylcyclohexane product having one of the following general formulas:

Formula IX: ???????? (H ₂ C═CH) ₂ C ₆ H ₉ CH ₂ CH ₂ -Si (OR) ₃

Formula _{X: (H 2 C = CH} ) 2 C 6 H 9 CH 2 CH 2 -SiR 3

Formula XI: ???????? (H ₂ C═CH) ₂ C ₆ H ₉ CH ₂ CH ₂ -Y

In formulas IX and X, R represents a branched or linear C1-C20 alkyl, C3-C20 cycloaliphatic or aromatic group. The groups need not all be the same in a single molecule. That is, in formula X, one R group may be octyl, the other R group may be methyl, and the third R group may be tert-butyl. In preferred compounds of formula IX and formula X, R is methyl, ethyl or isopropyl.

Y represents a branched or linear C1-C20 alkyl, a C3-C20 cycloaliphatic or aromatic group, and x is 0 or greater than 0, wherein Y is a radical of the formula (XII), (XIII) or (XIV) ) ≪ / RTI > monovalent siloxane radicals:

Expression XII:

Expression XIII:

Equation XIV:

Examples of mono-hydrosilylated compounds of formula XI include (H ₂ C═CH) ₂ C ₆ H ₉ CH ₂ CH ₂ -Si [OSi (CH ₃ ) ₃ ] ₂ CH ₃ and (H ₂ C═CH) ₂ C ₆ H ₉ CH ₂ CH ₂ -Si (CH ₃ ) ₂ -O-Si (CH ₃ ) ₂ CH ₂ CH ₂ Si (CH ₃ ) ₃ .

Commercially available trivinylcyclohexane is mainly a mixture of stereoisomers having vinyl groups at positions 1, 2 and 4. However, stereoisomers having 1,2,3-vinyl substituents and 1,3,5-vinyl substituents are also known. The following description is based on a mixture of 1,2, 4-isomers, but these descriptions are generally applicable to mixtures of two other trisubstituted isomers as described above.

For 1,2,4-trivinylcyclohexane stereoisomers, the difference lies in the orientation of the vinyl groups relative to one another (the cis to trans) and the orientation to the cyclohexane ring (in the equatorial axis direction). This results in a total of eight stereoisomers that occur as the enantiomers of the four mirror pairs. The four pairs, each of which is diastereomers, can be separated from one another in the mixture by careful distillation. Separation by distillation does not occur between each pair of the brightomers. That is, four compositions can be obtained, wherein each composition is a racemic mixture of two enantiomeric thiomers. These four compositions are hereinafter referred to as Isomer A, Isomer B, Isomer C, and Isomer D, respectively. Where the designations A, B, C, or D are based on the order in which they are collected using multiple distillation columns, where A is first and D is the last. The structures of the four isomers A, B, C and D of 1,2,4-trivinylcyclohexane are as follows:

When the hydrosilylation of a non-distillated mixture of tribylcyclohexane stereoisomers, or of the individual distillation fractions labeled isomers A and B, is promoted with the catalyst of the present invention, the initial addition of the silyl group is preferential at the 4 position of the cyclohexane ring . This preference is particularly high in the stereoisomers in the A fractions. Thus, selective mono-hydrosilylation is realized, as well as regio selective mono-hydrosilylation at 4 positions. In contrast, the platinum-catalyzed hydrosilylation of trivinylcyclohexane causes random addition of silyl functional groups to the vinyl group without special priorities at the 1, 2 or 4 position.

The catalyst of the present invention, for example a catalyst of formula (I) or formula (XIX), is prepared from isomer A and triethoxysilane in a yield of at least 65 weight percent, preferably at least 75 weight percent, , 4- (2-triethoxysilyl-ethyl) cyclohexane. The weight ratio of the mono-hydrosilylation product to the bis-hydrosilylation product is greater than 2, preferably greater than 4, more preferably greater than 6. l, 2-divinyl, 4- (2-triethoxysilylethyl) cyclohexane are key intermediates useful for improving rolling resistance and abrasion resistance of automotive tires. Accordingly, the present invention provides a method useful for selectively producing such a key intermediate.

Thus, in one embodiment, the present invention relates to a method for selectively producing a mono-hydrosilylation product from a reaction mixture comprising silylhydride and 1,2,4-trivinylcyclohexane. The process comprises reacting trivinylcyclohexane with a silyl hydride in the presence of a complex of formula (I) or (XIX) wherein the alkenyl functionality in 1,2,4-trivinylcyclohexane The molar ratio of Si-H functional groups in the silyl hydride is between about 0.5 / 3 and about 1.1 / 3; Wherein the silyl group from the silylhydride is selectively added to the 4-position of 1,2,4-trivinylcyclohexane.

In connection with the method, the silyl hydride may be triethoxysilane. The trivinylcyclohexane may be a mixture of trivinylcyclohexane stereoisomers or trivinylcyclohexane isomer A and / or trivinylcyclohexane isomer B.

The following examples are intended to illustrate, but not to limit the scope of the invention in any way. Unless otherwise indicated, all parts and percentages are by weight and all temperatures are degrees Celsius.

Examples

Introduction:

Air and moisture sensitive operations were performed in an MBroun inert atmosphere drybox containing a refined nitrogen atmosphere using standard vacuum line, Schlenk and Canulla techniques.

Benzene-d ₆ was purchased from Cambridge Isotope Laboratories, purified from sodium metal under an argon atmosphere, and stored through 4 A molecular sieves. CDC1 ₃ was purchased from or purchased from Cambridge Isotophor Laboratories or used in distillation in calcium hydride. The complexes ( ^iPr PDI) Fe (N ₂ ) ₂ and ( ^iPr BPDI) Fe (N ₂ ) ₂ having the structures as shown below were prepared according to the method described by Bart, et al., J. Am. Chem. , 126, 13794 ". Methyl bis (trimethylsilyloxy) silane (MD ^H M), triethoxy silane, triethyl silane, 1-octene, styrene, N, N- dimethyl amine and allyl trivinyl cyclohexane was dried prior to use calcium hydride was ^{_{distilled, M vl D 120 M vl (}} SilForce ( trade name), SL6100, M ^V1: dimethyl vinyl siloxy; D: dimethylsiloxy) and ^{_{MD 15 D H 30 M (SilForce}} SL6020, M: when trimethylsiloxy; D: Dimethylsiloxy; D: methylhydridosiloxy) was dried under reduced pressure for 12 hours.

¹ H NMR spectra were recorded on a Varian Inova 400 and 500 spectrometer operating at 399.780 and 500.62 MHz, respectively. All published chemical shifts are shifts relative to SiMe ₄ using the ¹ H (residual) chemical shifts of the solvent as a secondary standard.

GC analysis was performed using a Shimadzu GC-2010 gaschromatograph equipped with a Shimadzu AOC-20s autosampler and a Shimadzu SHRXI-5MS capillary column (15m x 250um) . The instrument was set at 1 [micro] l injection volume, inlet split ratio of 100: 1, inlet temperature of 120 [deg.] C and 250 [deg.] C and detector temperature, respectively. UHP-class helium was used as the carrier gas and the flow rate was 1.12 mL / min. The temperature program used for this analysis was set as follows: 80 캜, 1 min; 20 占 폚 / min to 240 占 폚, 4 minutes.

All hydrosilylation reactions were carried out at 23 < 0 > C unless otherwise specified.

Example  One. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with Methylbis ( Trimethylsilyloxy ) Silane  (MD ^H M) to give 1- Octane Hydrosilylation

In a nitrogen-filled dry box, 335 mg (2.99 mmol) of 1-octene and 665 mg (2.99 mmol) of MD ^H M were added to a 20 mL scintillation vial d. The solution was added with ( ^iPr PDI) Fe (N ₂ ) ₂ of 1 mg (0.002 mmol, lxlO ³ ppm catalyst loading) with stirring. After 15 minutes, the reaction was quenched by exposure to air. GC analysis of the product showed 99% conversion of 1-octene (retention time = 1.33 min) to the hydrosilylation product (retention time = 5.85 min). NMR analysis of the sample in benzene-d ₆ showed a signature peak for a-hydrogen at 0.62 ppm.

Example  2. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with With triethoxysilane  One- Octane Hydrosilylation

In a nitrogen-filled dry box, 245 mg (2.18 mmol) of 1-octene and 360 mg (2.19 mmol) of triethoxysilane were added to a 20 mL scintillation vial. This solution was added with 1 mg (0.002 mmol, 2x10 ³ ppm catalyst) of ( ^iPr PDI) Fe (N ₂ ) ₂ with stirring. After 15 minutes, the reaction was stopped by exposure to air. GC analysis of the product showed 99% conversion of 1-octene (retention time = 1.33 min) to the hydrosilylation product (retention time = 5.97 min).

Example  3. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with With triethylsilane  One- Octane Hydrosilylation

In a nitrogen-filled dry box, 290 mg (2.58 mmol) of 1-octene and 310 mg (2.67 mmol) of triethylsilane were added to a 20 mL scintillation vial. While stirring the solution, 1 mg (0.002 mmol, 2x10 ³ ppm catalyst charge) of ( ^iPr PDI) Fe (N ₂ ) ₂ group was added. After 60 minutes, the reaction was stopped by exposure to air. GC analysis of the product showed a 4% conversion of 1-octene (retention time = 1.33 min) to the hydrosilylation product (retention time = 5.88 min).

Example  4. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with Methylbis ( Trimethylsilyloxy ) Silane  (MD ^H M) of styrene Hydrosilylation

In a nitrogen-filled dry box, 190 mg (1.83 mmol) of styrene and 410 mg (1.84 mmol) of MD ^H M were added to a 20 mL scintillation vial. The solution is _{^{(iPr PDI) Fe (N 2}} ) 2 in the ^{1 mg (0.002 mmol, 2xl0 3} ppm catalyst charged) was added with stirring. After 60 minutes, the reaction was stopped by exposure to air. GC analysis of the product showed 3% conversion of the hydrosilylation product (retention time = 6.35 min) to styrene (retention time = 1.84 min).

Example  5. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with Methylbis ( Trimethylsilyloxy ) Silane  (MD ^H M), N, N- Dimethylallylamine Hydrosilylation

A nitrogen-filled dry box in, 20mL scintillation the MD ^H M was added in N, N- dimethyl-allylamine and 435 mg (1.96 mmol) of 165 mg (1.94 mmol) in a vial. The solution is _{^{(iPr PDI) Fe (N 2}} ) 2 in the ^{1 mg (0.002 mmol, 2xl0 3} ppm catalyst charged) was added with stirring. After 60 minutes, the reaction was stopped by exposure to air. NMR analysis of the product showed 93% conversion of N, N-dimethylallylamine to the hydrosilylation product (delta _{alpha -H} = 0.63 ppm).

Example  6. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with Methylbis ( Trimethylsilyloxy ) Silane  (MD ^H M), N, N- Dimethylallylamine  ( DMAA )of Hydrosilylation

Nitrogen - was charged with ^H MD M in the filled dry box, DMAA and 0.104 g (0.47 mmol) of 0.040 g (0.47 mmol) in 20mL scintillation vial. To this solution was added 0.003 g (0.005 mmol, 1 mol% catalyst charge) of ( ^iPr PDI) Fe (N ₂ ) ₂ with stirring.

After 60 minutes, the reaction was stopped by exposure to air. NMR analysis of the product showed 93% conversion of N, N-dimethylallylamine to the hydrosilylation product.

Example  7. ( ^iPr PDI ) Fe ( N ₂ ) ₂ Using With triethoxysilane  N, N- Dimethylallylamine  (DMAA) Hydrosilylation

The reaction in Example 6, except for using 0.040 g of DMAA, 0.077 g tetraethoxysilane and 0.003 g (0.005 mmol) in the tree (0.047 mmol) of ^{(0.47 mmol) (iPr PDI)} Fe (N 2) 2 ≪ / ^RTI &^gt; of DMAA and MD &^lt; ^{RTI ID = 0.0} &^gt; ^H M. ≪ / ^RTI &^gt; After 60 minutes, the reaction was stopped by exposure to air. NMR analysis of the product showed> 95% conversion of N, N-dimethylallylamine to the hydrosilylation product.

Example  8. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with With triethylsilane  N, N- Dimethylallylamine  (DMAA) Hydrosilylation

Of this reaction is 0.040 g (0.47 mmol) DMAA, 0.055 g (0.047 mmol) triethylsilane and 0.003 g (0.005 mmol) of _{^{(lw PDI) Fe (N 2}} ) embodiment, except that the ₂ Example 6 of the DMAs and MD &^lt; ^{RTI ID = 0.0} &^gt; ^H M. ≪ / ^RTI &^gt; After 60 minutes, the reaction was stopped by exposure to air. NMR analysis of the product showed that the conversion of N, N-dimethylallylamine to the hydrosilylation product was about 3% and the conversion to N, N-dimethyl-1-propenylamine was 8%.

Example  9. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with With triethoxysilane  Styrene Hydrosilylation

In a nitrogen-filled dry box, 45 mg (0.43 mmol) of styrene and 71 mg (0.43 mmol) of triethoxysilane were added to a 20 mL scintillation vial. 2 mg (0.004 mmol, 1 mol%) of ( ^iPr PDI) Fe (N ₂ ) ₂ was added while stirring the solution. After 60 minutes, the reaction was stopped by exposure to air. NMR analysis of the product showed> 95% conversion of styrene to the hydrosilylation product.

Example  10. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with With triethylsilane Trivinylcyclohexane  (Isomer A) Hydrosilylation

In a nitrogen-filled drybox, 349 mg (2.15 mmol) of trivinylcyclohexane and 251 mg (2.16 mmol) of triethylsilane were added to a 20 mL scintillation vial. This solution was added with 1 mg (0.002 mmol, 2x10 ³ ppm catalyst) of ( ^iPr PDI) Fe (N ₂ ) ₂ with stirring. After 60 minutes, the reaction was stopped by exposure to air. GC analysis of the product showed that the conversion of trivinylcyclohexane to the hydrosilylation product was 3.5%, of which 3.2% was the monosilylated product. The C ₄ -vinylhydrosilylation product (retention time = 7.89 min) was 87% of the monosilylated product.

Example  11. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with Methylbis ( Trimethylsilyloxy ) Silane  (MD ^H M) Trivinylcyclohexane  (Isomer A) Hydrosilylation

Nitrogen-charged in the dry box, a 20mL scintillation MD ^H M of trivinyl cyclohexane and 347 mg (1.56 mmol) of the vial 253 mg (1.56 mmol) was added to. Next, 1 mg (0.002 mmol, 2x10 ³ ppm catalyst packed) of ( ^iPr PDI) Fe (N ₂ ) ₂ was added to the reaction mixture. After stirring for 60 minutes, the reaction was stopped by exposure to air. GC analysis of the product showed that the conversion of trivinylcyclohexane to the hydrosilylation product was 58%, of which 95% was the monosilylated product. The C ₄ -vinylhydrosilylation product (retention time = 7.61 min) was 95% of the monosilylated product.

Example  12. ( ^iPr PDI ) Fe ( N ₂ ) ₂ use with With triethoxysilane Trivinylcyclohexane  (Isomer A) Hydrosilylation

This reaction is of trivinyl cyclohexane, silane and 1 mg (0.002 mmol, 2x10 ppm catalyst charge) to the tree of 302 mg (1.84 mmol) of ^{298 mg (1.84 mmol) (iPr} PDI) Fe (N 2) 2 is Was carried out in the same manner as the hydrosilylation with MD ^H M as shown in Example 4, GC analysis of the product showed that the conversion of trivinylcyclohexane to the hydrosilylation product was 90%, of which 82% was the monosilylated product. The C ₄ -vinylhydrosilylation product (retention time = 7.80 min) was 94% of the monosilylated product. The weight ratio of monohydrosilylation product to bishydrosilylated product was > 8.

compare Example  A. [( ^{2,6 ~ Et2} PDI ) Fe ( N ₂ )] ₂ [[mu] - N ₂ )]use with Triethoxysilane  (TES) TVCH  The mono- Hydrosilylation

The 1,2,4-trivinylcyclohexane sample used in this experiment contained 98.4% Isomer A and 1.6% Isomer B. TES was prepared by the direct process described in U.S. Patent No. 7,429,672. Was prepared in the ^{[(2,6 ~ Et2 PDI) Fe} (N 2)] 2 [μ- (N 2)] is the method described in Example 3 of U.S. Patent Application Publication No. 2011/0009573.

In an inert atmosphere at 23 占 폚, 0.150 g (0.92 mmol) of 1,2,4-trivinylcyclohexane and 0.150 g (0.92 mmol) of TES were added to the scintillation vial. The SiH / vinyl molar ratio was 1/3. 0.002 g (0.002 mmol) of [( ^2,6-Et ₂ PDI) Fe (N ₂ )] ₂ [μ- (N ₂ )] (0.5 mol% catalyst for silane) was added while stirring the solution. A fever occurred. The reaction was carried out with stirring for 60 minutes and was stopped by exposure to air. GC and GC / MS analysis of the reaction mixture proved that the TES was completely consumed and the mono- and bis-hydrosilylation products were 60.2% and 24.4%, respectively. The weight ratio thereof was 2.46.

By proton NMR analysis, the mono-hydrosilylation revealed 90% regio selectivity in the vinyl group at the 4-position of the cyclohexane ring.

compare Example  B. Casted Pt  Comparative experiment using catalyst

Trimethoxysilane and 1,2,4-trivinylcyclohexane were synthesized from triethoxysilane and 1,2,4-trivinylcyclohexane using the method described in Example 1 of U.S. Patent No. 7,696,269 to (2 -Triethoxysilylethyl) divinylcyclohexane. ≪ / RTI > To a 5 liter, 3-neck round bottom flask equipped with a heating mantel, mechanical stirrer, addition funnel, Friedrich condenser, nitrogen inlet and thermocouple / thermostat was charged 1800 grams (11.1 moles) of TVCH and 100 grams of casted platinum 3.6 g (1 wt% Pt) of the catalyst solution was added thereto. The contents of the flask were heated to 90 DEG C with stirring. Then triethoxysilane (1641 g, 9.99 moles) was slowly added over 4 hours via an addition funnel to control the exotherm. During the addition, the temperature was maintained at 101 - 109 ° C. In this reaction, the SiH / vinyl molar ratio was 0.3. GC analysis showed that the crude reaction product contained 21 wt% unreacted TVCH, 48 wt% mono-hydrosilylation product, ((2-triethoxysilylethyl) divinylcyclohexane), 26.3 wt% bis hydrosilylated trivinyl cyclo Hexane and 2.7 wt% tris hydrosilylated trivinylcyclohexane. The weight ratio of mono to bis was 1.82.

GC analysis of the reaction product from the platinum-catalysed trivinylcyclohexane hydrosilylation described above showed three closely spaced peaks of approximately the same intensity separated by the residence time corresponding to the mono-hydrosilylation product. This contrasts with the reaction product obtained with the non-noble metal-based pyridine diimine catalyst of the present invention. When the catalyst of the present invention is used, typically one peak corresponding to the position by silylation of the vinyl group at the 4-position of the cyclohexane ring dominates this residence time portion of the gas chromatogram. Thus, it can be concluded that platinum catalysis allows hydrosilylation of three vinyl groups with almost the same probability. That is, the platinum catalysis does not provide the position selectivity realized with the non-noble metal pyridine diimine catalyst of the present invention.

Example  13. ( ^iPr PDI ) Fe ( N ₂ ) ₂ Using M ^vi D ₁₂₀ M ^vi  ( SilForce SL6100 )and MD ₁₅ D ' ₃₀ M  (SilForce SL6020 ) Crosslinking

In a nitrogen filled dry box, a 20 mL scintillation vial was charged with 1.0 g of SilForce SL6100 and 44 mg of SilForce SL6020. A preservation solution of 1 mg ( ^iPr PDI) Fe (N ₂ ) ₂ in 200 mg toluene was prepared and added dropwise to the stirred solution of the polymers. Immediate gelation of the polymers was observed, and a hard gel was obtained at the end of the addition of the catalyst. This product was not different from that obtained using casted catalyst.

Example  14. ( ^iPr BPDI ) Fe ( N ₂ ) ₂ use with With triethoxysilane  Styrene Hyde Silylation

In a nitrogen-filled dry box, 45 mg (0.43 mmol) of styrene and 71 mg (0.43 mmol) of triethoxysilane were added to a 20 mL scintillation vial. To this solution was added 3 mg (0.004 mmol, 30 x 10 ³ ppm catalyst) of ( ^iPr BPDI) Fe (N ₂ ) ₂ with stirring. After 60 minutes, the reaction was stopped by exposure to air. NMR analysis of the product showed a 30% conversion of styrene to the hydrosilylation product.

Example  15. ( ^iPr BPDI ) Fe ( N ₂ )use with With triethoxysilane  N, N- Dimethylallylamine  ( DMAA )of Hydrosilylation

This reaction was carried out in a similar manner to the hydrosilylation reaction of triethoxysilane and styrene. 35 mg (0.41 mmol) of DMAA, 68 mg (0.41 mmol) of triethoxysilane and 3 mg (0.004 mmol, 30 x 10 ³ ppm catalyst) of ( ^iPr BPDI) Fe (N ₂ ) ₂ were used. NMR analysis of the product showed that the conversion of DMAA to the hydrosilylation product was > 95%.

Example  16. ( ^iPr BPDI ) Fe ( N ₂ ) ₂ use with, With triethoxysilane Trivinylcyclohexane  (Isomer A) Hydrosilylation

In a nitrogen-filled dry box, 100 mg (0.616 mmol) of trivinylcyclohexane and 102 mg (0.621 mmol) of triethoxysilane were added to a 20 mL scintillation vial. Next, 2 mg (0.003 mmol, 10 x 10 ³ ppm catalyst loaded) of ( ^iPr BPDI) Fe (N ₂ ) ₂ was added to the reaction mixture. After stirring for 60 minutes, the reaction was stopped by exposure to air. GC analysis of the product showed that the conversion of trivinylcyclohexane to the hydrosilylation product was 85%, of which 95% was the monosilylated product. The C ₄ -vinylhydrosilylation product (retention time = 7.61 min) was 94% of the monosilylated product.

While the foregoing description contains many specific embodiments, it should be understood that these specific embodiments are not to be construed as limiting the scope of the invention, but merely as exemplifying preferred embodiments of the invention. It will be appreciated by those skilled in the art that many other modifications within the spirit and scope of the invention as defined in the appended claims will be possible.

Claims (34)

(i) contacting a composition comprising silyl hydride and at least one unsaturated group-containing compound with a complex of formula (I) in the presence or absence of a solvent, wherein said silyl hydride is present in said at least one unsaturated group- To produce a hydrosilylation product comprising said complex,

(Formula I)
(Wherein: G is Mn, Fe, Ni, or Co, and; x is O or l, and; each _{R 1, R 2, R 4} , R 5, R 6, R 7, R 8 And R _9` are independently H, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group; Each R ₃ is independently H, C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, or an inert functional group, wherein R ₁ to R ₉ other than hydrogen optionally contain at least one heteroatom; Each R ₁₀ is C ₁ -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl or substituted aryl group, optionally containing at least one heteroatom; Any _two of which are optionally adjacent to each other of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may be substituted or unsubstituted, saturated or unsaturated To form a ring which is a cyclic structure); And
(ii) optionally optionally removing said complex from said hydrosilylation product,
Here, the silyl hydride is ^{_{R 3 a (R 4 0)}} b SiH ( formula _Ⅱ), Q _u T _v T _p ^H D _w D ^H _x M ^H _y M _z (formula _{Ⅲ), R 3 Si (CH} 2 ) _f SiR ₂ O _e SiR ₂ H (Formula XX), (RO) ₃ Si (CH ₂ ) _f (SiR ₂ O) _e SiR ₂ H (Formula XXI), and combinations thereof Being; Wherein Q is Si0 _4/2, T is a R'Si0 _3/2 and, T ^H is HSi0 _3/2, and, D is R _'2 Si0 _2/2, and, D is ^H R'HSi0 _2/2, M is ^H H _g R _{'3 -,} and _g Si0 _1/2, M is R' ₃ Si0 _1/2 a. Each R ³ , R ⁴ and R 'is independently selected from the group consisting of C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl, or substituted aryl wherein R ³ , R ⁴ and R'; a and b are integers of from 0 to 3, with the proviso that a + b = 3; f has a value of 1 to 8, e has a value of 1 to 11, each g has a value of 1 to 3, p is 0 to 20, u is 0 to 20, v is 0 to 20 Y is from 0 to 20 and z is from 0 to 20 with the proviso that p + x + y is from 1 to 3000 and that all elements of the silylhydride are Presuming that the valence is satisfied,
The at least one unsaturated group-containing compound is selected from the group consisting of alkene, C2-C18 olefins, cycloalkenes, unsaturated cycloalkanes, unsaturated cycloalkenes, unsaturated cycloalkyl epoxides, unsaturated alkyl epoxides, end unsaturated amines, unsaturated aromatic hydrocarbons, Selected from the group consisting of allyl polyether, unsaturated aryl ethers, vinyl-functionalized silanes, vinyl-functionalized silicones, terminally unsaturated acrylates or methyl acrylates, terminally unsaturated polyurethane polymers,
However, when the complex of formula (I) is iron, bis (dinitrogen) [N, N '- [(2,6-pyridinediyl 虜 N) diethylidine] bis [2,6- Benzeneamine-kappa]] -, (SP-5-13) -coordinate compound and the silylhydride is triethylsilane, the at least one unsaturated group-containing compound is an alkyl capped allyl polyether or styrene; And the complex of formula (I) is selected from the group consisting of iron, bis (dinitrogen) [N, N '- [(2,6-pyridinediyl 虜 N) diethylidine] bis [2,6- Amine-kappa]] -, (SP-5-13) -coordinate compound, and if the silylhydride is methylbis (trimethylsilyloxy) silane, the at least one unsaturated group-containing compound is an alkyl capped allyl polyether Assuming that it can not be,
Silyl hydride, and at least one unsaturated group-containing compound. 2. The method of claim 1, comprising removing the complex from the hydrosilylation product by magnetic separation, filtration and / or extraction. 3. The compound of claim 1 wherein each R < ₁₀ > is independently

Wherein R ₁ , R ₂ , R ₄ , R ₅ , and R ₆ are as defined in claim 1. 2. The process of claim 1 wherein R < ₁ > and R < ₂ > are isopropyl groups. 2. The method of claim 1 wherein R < ₃ > is methyl. 2. The method of claim 1, wherein G is Fe. The method of claim 1, wherein the complex is immobilized on a support. According to claim 1, in which the carrier is selected from carbon, silica, alumina, MgCl _2, zirconia, polyethylene, polypropylene, polystyrene, poly (aminostyrene), dendritic polymer (dendrimers), and the group consisting of a combination thereof, Way. The method according to claim 8, wherein at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ comprises a functional group covalently bonded to the carrier. 2. The method of claim 1, wherein each p, u, v, y, and z is independently 0 to 10, w and x are independently 0 to 100, and p + x + y is 1 to 100. The method of claim 1, wherein the silyl hydride has the structure of formula (IV) or formula (V)

(Formula IV)

(Formula V)
Wherein each R ⁷ , R ⁸ and R ⁹ is independently C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl, or substituted aryl, and R ⁶ is hydrogen, C1-C18alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, and x and w are independently 0 or greater than 0). The method of claim 1 wherein the silyl hydride _{(CH 3 0) 3 SiH,} (C 2 H 5 0) 3 SiH, (CH 3) 3 SiOSi (CH 3) 2 H, [(CH 3) 3 SiO] ₂ SiH (CH ₃ ), [(CH ₃ ) ₂ SiO] ₃ OSiH (CH ₃ ) and [(CH ₃ ) ₂ SiO] ₄ OSiH (CH ₃ ). The method of claim 1, wherein said at least one unsaturated group-containing compound is selected from the group consisting of a compound of formula (XVII), a compound of formula (XVIII)
R ³ _a SiR ¹² _{4 -a} (Formula XV II)
Q _u T _v T _p ^vi D _w D ^vi _x M ^vi _y M _z (Formula XVIII)
(Wherein, Q is Si0 _4/2 and, T is R'Si0 _3/2 and, T ^vi is R ¹² Si0 _3/2, and, D is R _'2 and Si0 _2/2, D ^vi is R'R ¹² an Si0 _2/2, M ^vi is R ¹² _g R _{'3 - g} and SiOi / _2, M is R' ₃ Si0 _1/2 a; R ¹² is a vinyl gt; each of R ³ and R 'are independently C1 Wherein R < ³ > and R <'> optionally comprise at least one heteroatom, a has a value of from 1 to 3, each g is an integer from 1 to 3, P is from 0 to 20, u is from 0 to 20, v is from 0 to 20, w is from 0 to 5000, x is from 0 to 5000, y is from 0 to 20, z Is 0 to 20, provided that v + p + w + x + y is 1 to 10,000, and that all the elements in the at least one unsaturated group-containing compound satisfy its valence. 3. The composition of claim 1, wherein said at least one unsaturated group-containing compound is selected from the group consisting of 1-octene, trivinylcyclohexane, styrene, alkyl capped allyl polyether, NN-dimethylallylamine, ≪ / RTI > and combinations thereof.

(Wherein each R ₁₁ is independently C1-C18 alkyl, C1-C18 substituted alkyl, vinyl, aryl, or substituted aryl and n is 0 or greater than 0). A composition prepared by the method of claim 1, wherein said unsaturated group-containing compound is an end unsaturated amine, said composition essentially lacking unreacted terminal unsaturated amine and isomerization product, said product having an internal addition products are essentially free and said composition comprises a complex of formula (I). 7. A composition produced by the method of claim 1, wherein said at least one unsaturated group-containing compound is vinyl-functional silicone, and said composition comprises a complex of formula (I). Contacting a composition comprising silyl hydride and a polyunsaturated compound with a complex of formula (I) or (XIX) to form a polyunsaturated compound having at least one unsaturated group in the polyunsaturated compound by reacting the polyunsaturated compound with the silyl hydride To yield a mono-hydrosilylation product by causing a selective hydrosilylation to occur,

(Formula I)

(Formula XIX)
(Wherein G is Mn, Fe, Ni, or Co; x is 0 or 1; each of R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R _7, R ₈ and R ₉ are independently H, C1-C18 alkyl, C1-C18 substituted alkyl, aryl, substituted aryl, or an inert functional group; each R ₃ is independently H, C1-C18 alkyl, C1- C18 substituted alkyl, or an inert functional group, wherein R ₁ to R ₉ other than hydrogen optionally contain at least one heteroatom; each R ₁₀ is independently selected from the group consisting of C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, a substituted aryl group, wherein R10 contains at least one heteroatom in any optional and; each R ₁₅ is aryl or substituted aryl; any optionally _{R 1, R 2 R 3,} R 4, R 5, R 6 , Any two adjacent to each other in R ₇ , R ₈ , R ₉ and R ₁₀ may form a ring of a substituted or unsubstituted, saturated or unsaturated cyclic structure together);
The polyunsaturated compound is represented by formula (VII) or formula (VIII)
E ¹ [(CH ₂ ) _β CR ¹ = CH ₂ ] _α (Formula VII)
R ² _? E ² [(CH ₂ ) _? CR ¹ = CH ₂ ] _? (Formula VIII)
Wherein E ¹ is a divalent or polyvalent aliphatic or aromatic cyclic hydrocarbon group containing 3 to 25 carbon atoms or a divalent or polyvalent aliphatic or aromatic heterocyclic group containing 3 to 25 carbon atoms, cyclic hydrocarbon, wherein the heteroatoms are oxygen, nitrogen, silicon and is selected from the group consisting of sulfur; E ² is from 3 to 8 silicon atoms and 3 to include the oxygen atom of the 8, and a divalent or cyclic approach with silicon Each R ¹ and R ² is independently hydrogen or a hydrocarbon group containing from 1 to 8 carbon atoms, each of?,? And? Is independently an integer,? Is 2 to 6,? Is 0 to 6; and y is 0 to 4;
Wherein the mole ratio of Si-H functional groups in the silylhydride to alkenyl functionality in the unsaturated compound is between about 0.5 / alpha and about 1.1 / alpha,
A process for the selective preparation of a mono-hydrosilylation product from a composition comprising silyl hydride and a polyunsaturated compound. 18. The method of claim 17, wherein the molar ratio of Si-H functional groups in the silylhydride to alkenyl functionality in the unsaturated compound is about 1 / a. 18. The method of claim 17, wherein the unsaturated compound is selected from the group consisting of trivinylcyclohexane, tetravinylcyclobutane, trivinyltrimethylcyclotrisiloxane, tetramethyltetravinylcyclotetrasiloxane, triallyl cyanurate, and triallyl isocyanurate. Selected from the military. Way. 18. The method of claim 17, wherein the unsaturated compound is trivinylcyclohexane. The method of claim 17, wherein the silyl hydride has one of the structures of formula (II), formula (IV), or formula (V)
R ³ _a (R ⁴ 0) _b SiH (formula II),

(Formula IV)

(Formula V)
Wherein R ³ , R ⁴ , R ⁷ , R ⁸ and R ⁹ are each independently C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl or substituted aryl, R ⁶ is hydrogen, X and w are independently 0 or greater than 0, a and b are integers from 0 to 3 with the proviso that a + b = 3 and x is 0 or less than 0, Assuming a big one). 18. The method of claim 17 wherein the silyl hydride _{(CH 3 0) 3 SiH,} (C 2 H 5 0) 3 SiH, (CH 3) 3 SiOSi (CH 3) 2 H, [(CH 3) 3 SiO] ₂ SiH (CH ₃ ), [(CH ₃ ) ₂ SiO] ₃ OSiH (CH ₃ ) and [(CH ₃ ) ₂ SiO] ₄ OSiH (CH ₃ ). 18. The compound of claim 17 wherein each R < ₁₀ > is independently

Wherein R ₁ , R ₂ , R ₄ , R ₅ , and R ₆ are as defined in claim 17. 18. The method of claim 17, wherein the complex is immobilized on a carrier. A composition prepared by the method of claim 17 comprising a mono-hydrosilylation product and a bis-hydrosilylation product, wherein the weight ratio of the mono-hydrosilylation product to the bis-hydrosilylation product is greater than about 1.8, Lt; RTI ID = 0.0 > (I). ≪ / RTI > 26. The composition of claim 25, wherein the weight ratio of the mono-hydrosilylation product to the bis-hydrosilylation product is greater than about 3. 26. The composition of claim 25, wherein the weight ratio of the mono-hydrosilylation product to the bis-hydrosilylation product is greater than about 4. 26. The composition of claim 25 comprising monosilylated divinylcyclohexane having the general formula:
Formula IX: ???????? (H ₂ C═CH) ₂ C ₆ H ₉ CH ₂ CH ₂ -Si (OR) ₃
Formula _{X: (H 2 C = CH} ) 2 C 6 H 9 CH 2 CH 2 -SiR 3
Formula XI: ???????? (H ₂ C═CH) ₂ C ₆ H ₉ CH ₂ CH ₂ -Y
(Wherein each R is independently a C1-C20 alkyl, a C3-C20 aliphatic or aromatic cyclic hydrocarbon group, and Y is
Expression XII:

XIII

Equation XIV:

Wherein each R is independently a C1-C20 alkyl, a C3-C20 aliphatic or aromatic cyclic hydrocarbon group, and x is 0 or greater than 0). Reacting 1,2,4-trivinylcyclohexane with silyl hydride in the presence of a complex of formula (I) or (XIX)

(Formula I)

(Formula XIX)
R, R _2, R ₄ , R ₅ , R ₆ , R ₇ , R ₈ and R ₉ are independently selected from the group consisting of H, Wherein each R ₃ is independently H, C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, or an inert functional group, wherein each R ₃ is independently selected from the group consisting of hydrogen, C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl, substituted aryl, other than R ₁ to R ₉ is any optionally contains at least one hetero atom; and each R ₁₀ is C1-C18 alkyl, C1-C18 substituted alkyl, aryl or substituted aryl group, wherein R ₁₀ is in any optional contains at least one hetero atom; each R ₁₅ is aryl or substituted aryl; any optionally _{R 1, R 2 R 3,} R 4, R 5, R 6, R 7, R 8, R 9 and R ₁₀ may form a ring of substituted or unsubstituted, saturated or unsaturated cyclic structure together);
The mole ratio of Si-H functional groups in the silylhydride to the alkenyl functionality in the 1,2,4-trivinylcyclohexane is between about 0.5 / 3 and about 1.1 / 3;
Wherein the silyl group from the silyl hydride is selectively added to the 4-position of the 1,2,4-trivinylcyclohexane,
A process for the selective preparation of a mono-hydrosilylation product from 1,2,4-trivinylcyclohexane and silyl hydride. 30. The method of claim 29, wherein the silyl hydride is triethoxysilane. 30. The method of claim 29, wherein the silyl hydride is bis (trimethylsiloxy) methyl silane. 30. The method of claim 29, wherein the trivinylcyclohexane is a mixture of trivinylcyclohexane stereoisomers. The process of claim 29, wherein the trivinylcyclohexane is trivinylcyclohexane isomer A, trivinylcyclohexane isomer B, or a mixture thereof, and isomer A and isomer B are the structures of structures (XV) and (XVI) Lt; / RTI >

(i) contacting a composition comprising silyl hydride and at least one unsaturated group-containing compound with a complex of formula (XIX) in the presence or absence of a solvent to react said silylhydride with said at least one unsaturated group- To form a hydrosilylation product comprising said complex; And

(Formula XIX)
R is selected from the group consisting of R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R _8, And R ₉ are independently H, C 1 -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl, substituted aryl, or an inert functional group; Each R < ₁₅ > is aryl or substituted aryl; R ₁ , R ₂ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R 15 other than hydrogen optionally contain at least one heteroatom; Each R ₁₀ is C ₁ -C 18 alkyl, C 1 -C 18 substituted alkyl, aryl or substituted aryl group, wherein R ₁₀ optionally contains at least one heteroatom; Any _two of R ₁ , R ₂ , R ₁₅ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ and R ₁₀ may optionally together form a substituted or unsubstituted, saturated or unsaturated cyclic structure Lt; / RTI > And
(ii) optionally optionally removing said hydrosilylation product,
The silyl hydride formula ^{(XXⅡ) (R 4 0)} 3 SiH ( wherein each R ⁴ is independently C1-C18 alkyl, C1-C18 substituted alkyl, aryl, or substituted aryl, R ⁴ is in any optional Containing at least one heteroatom;
Wherein the at least one unsaturated group-containing compound is selected from the group consisting of terminal unsaturated amines, unsaturated aromatic hydrocarbons, unsaturated cycloalkanes, and combinations thereof.
A hydrosilylation method of a composition comprising silyl hydride and at least one unsaturated group-containing compound